Cleaning compositions containing hydroxy mixed ethers, methods of preparing the same, and uses therefor

ABSTRACT

Cleaning compositions containing hydroxy mixed ethers of the general formula (I) are described:  
     R 1 O[CH 2 CHR 4 O] x [CH 2 CHR 3 O] y CH 2 CH(OH)R 2   (I)  
     wherein R 1  represents an alk(en)yl radical having from 4 to 22 carbon atoms; R 2  represents an alk(en)yl radical having from 2 to 22 carbon atoms; R 3  represents a hydrogen or a methyl radical; R 4  represents a hydrogen or a methyl radical; x is from 1 to 40; y is from 1 to 40; and x+y&gt;=1; and wherein the alkylene units —CH 2 CHR 3 O— and —CH 2 CHR 4 O— are in randomized form, preferably in an ethylene oxide to propylene oxide ratio of from 40:1 to 40:5. Methods of preparing and using the hydroxy mixed ethers are also described.

BACKGROUND OF THE INVENTION

[0001] Compositions for washing and cleaning hard nontextile surfaces inthe household and commercial sector are generally intended to develop asmall foam volume on use, which further reduces significantly within afew minutes. Compositions of this kind have been known for a long timeand are established on the market. They essentially comprise aqueoussurfactant solutions of different kinds with or without the addition ofbuilders, solubilizers (hydrotropes) or solvents. At the beginning ofcleaning work, the consumer does in fact desire a certain foaming of theapplication solution, for the purpose of demonstrating effectiveness,but the foam ought rapidly to collapse so that areas once cleaned neednot be wiped again. For this purpose, the compositions-of the typementioned are normally formulated with low-foaming nonionic surfactants.

[0002] For machine-washed kitchen- and tableware, more stringentrequirements are nowadays imposed than for handwashed ware. Forinstance, even ware fully cleaned of its food residues is consideredimperfect if, following machine washing, it still has whitish spots,originating from water hardness or other mineral salts, which derivefrom dried-on water droplets for lack of wetting agents. In order toobtain spotless ware with a clear luster, therefore, rinse aids areused. The addition of liquid or solid rinse aid, which may be addedseparately or may already be present in a ready-to-use presentation formtogether with the detergent and/or regenerating salt (“2 in 1”, “3 in1”, e.g., in the form of tabs and powders), ensures that the water runsoff as fully as possible from the ware so that at the end of the washprogram the various surfaces are lustrous and free from residue.

[0003] Customary commercial rinse agents constitute mixtures of, forexample, nonionic surfactants, solubilizers, organic acids and solvents,water and, where appropriate, preservatives and fragrances.

[0004] The function of the surfactants in these compositions is toinfluence the surface tension of water in such a way that it is able torun off in an extremely thin coherent film from the ware so that nowater droplets, streaks or films remain in the subsequent drying process(the effect referred to as wetting).

[0005] Accordingly, surfactants in rinse aids are also required tosuppress the foam which occurs as a result of food residues in thedishwasher. Since the rinse aids usually include acids for enhancing thedry-clear effect, the surfactants used must also be relativelyhydrolysis-insensitive to acids. Rinse aids are used both in thehousehold and in the commercial sector. In domestic dishwashers, therinse aid is normally metered in after the prewash cycle and cleaningcycle at just 40° C.-65° C. The commercial dishwashers operate with onlyone wash liquor, which is refreshed only by addition of the rinsesolution from the preceding wash. Throughout the entire wash program,therefore, the water is never completely replaced. Accordingly, therinse aid must also have a foam suppressing effect, must betemperature-stable at a sharp temperature gradient of 85-35° C., andmust also be sufficiently stable toward alkali and active chlorine.

[0006] The German laid-open specification DE 19738866 describessurfactant mixtures comprising hydroxy mixed ethers and nonionicsurfactants, such as fatty alcohol polyethylene glycol/polypropyleneglycol ethers, where appropriate with endgroup capping, which exhibitvery good foaming behavior and display outstanding rinse-clear effectsin rinse agents.

[0007] From the German laid-open specification DT 2432757 it is knownthat hydroxy mixed ethers are used as foam suppressants in detergentsand cleaning products.

[0008] It was an object of the present invention to develop detergentsand cleaning products which combine good foaming and cleaning behavior,in particular a very good runoff behavior on plastic surfaces and highmaterial compatibility of the surfaces to be cleaned. Furthermore, theintention was to provide hydroxy mixed ethers which can be incorporatedwith particular advantage into solid formulations.

[0009] The object has been achieved by developing hydroxy mixed etherswhich, in addition to their foam suppressing effect, also exhibit a highlevel of compatibility for plastic. Surprisingly, the hydroxy mixedethers of the invention are particularly notable for their colorless,clear appearance, which opens up the possibility of incorporation into alarge number of detergents and cleaning products without a complicatedbleaching operation.

SUMMARY OF THE INVENTION

[0010] The invention provides detergents and cleaning productscontaining hydroxy mixed ethers (HMEs) of the formula (I):

R¹O[CH₂CHR⁴O]_(x)[CH₂CHR³O]_(y)CH₂CH(OH)R²  (I)

[0011] in which R¹ stands for an alkyl and/or alkenyl radical havingfrom 4 to 22 carbon atoms; R² stands for an alkyl and/or alkenyl radicalhaving from 2 to 22 carbon atoms; R⁴ stands for hydrogen or a methylradical; R³ stands for hydrogen or a methyl radical; x is from 1 to 40;y is from 1 to 40; and x+y>=1, characterized in that the alkylene units[CH₂CHR⁴O] and [CH₂CHR³O] are in randomized form.

[0012] Preference is given to those hydroxy mixed ethers which containthe alkylene units [CH₂CHR⁴O] and [CH₂CHR³O], preferably ethylene oxideand propylene oxide, in “randomized” form, i.e., the prior mixing of thealkoxylation reagents and reaction with the alcohol and subsequentepoxide closure produces hydroxy mixed ethers which possess astatistical, random distribution of the alkylene units. Particularpreference is given to hydroxy mixed ethers containing ethylene oxideunits and propylene oxide units randomized in a ratio of from 40:1 to40:5.

DETAILED DESCRIPTION OF THE INVENTION

[0013] Hydroxy Mixed Ethers

[0014] Hydroxy mixed ethers are known from the literature and aredescribed, for example, in the German Patent Publication DE 19738866.

[0015] They are prepared by reacting 1,2-epoxyalkanes (R²CHOCH₂) inwhich R² stands for an alkyl and/or alkenyl radical having from 2 to 22,in particular from 6 to 16, carbon atoms with alkoxylated alcohols.

[0016] Preference is given in the context of the invention to thosehydroxy mixed ethers which derive from alkoxylates of monohydricalcohols of the formula R¹—OH having from 4 to 18 carbon atoms in whichR¹ stands for an aliphatic, saturated, straight-chain or branched alkylradical, in particular having from 6 to 16 carbon atoms.

[0017] Examples of suitable straight-chain alcohols are 1-butanol,caproyl, enanthyl, caprylyl, pelargonyl, and capryl alcohol,1-undecanol, lauryl alcohol, 1-tridecanol, myristyl alcohol,1-pentadecanol, palmityl alcohol, 1-heptadecanol, stearyl alcohol,1-nonadecanol, arachidyl alcohol, 1-heneicosanol, behenyl alcohol, andtheir technical-grade mixtures, such as are produced in thehigh-pressure hydrogenation of technical-grade methyl esters based onfats and oils. Examples of branched alcohols are those known as oxoalcohols, which carry usually from 2 to 4 methyl group branches and areprepared by the oxo process, and those known as guerbet alcohols, whichare branched with an alkyl group in position 2. Suitable guerbetalcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and/or2-octyldodecanol.

[0018] The alcohols are used in the form of their alkoxylates, which areprepared conventionally by reacting the alcohols in randomized sequencewith ethylene oxide and propylene oxide.

[0019] This results in hydroxy mixed ethers with EO and PO units inarbitrary sequence. Preference is given both to alkoxylates which areformed by reacting alcohol with mixtures of from 1 to 10 mol ofpropylene oxide (R⁴=methyl, x=1-10 or R³=methyl, y=1-10) and from 10 to40 mol of ethylene oxide (R³=hydrogen, y=10-40 or R⁴=hydrogen, x=10-40).

[0020] Preference in the context of the invention is given to thosehydroxy mixed ethers which derive from alkoxylates of monohydricalcohols of the formula R¹—OH having from 4 to 18 carbon atoms,preferably from 6 to 16 and in particular from 8 to 10 carbon atoms, inwhich R¹ stands for a linear or branched alkyl and/or alkenyl radical.

[0021] Very particular preference is given to hydroxy mixed ethers ofthe formula (I) in which R¹ stands for an alkyl radical having from 8 to10 carbon atoms, based in particular on a natural fatty alcohol, R²stands for an alkyl radical having 10 carbon atoms, in particular for alinear alkyl radical.

[0022] Alkyl and/or Alkenyl Oligoglycosides

[0023] In a further embodiment, the detergents and cleaning products ofthe invention comprise alkyl and/or alkenyl oligoglycosides of theformula (II)

R⁵O—[G]_(p)  (II)

[0024] in which R⁵ stands for an alkyl and/or alkenyl radical having 4to 22 carbon atoms, G for a sugar radical having 5 or 6 carbon atoms,and p for numbers from 1 to 10, are present.

[0025] They may be obtained by the relevant processes of preparativeorganic chemistry. As representatives of the extensive literature,reference may be made here to the review work by Biermann et al. inStarch/Stärke 45, 281 (1993), B. Salka in Cosm. Toil. 108, 89 (1993),and also J. Kahre et al. in SÖFW-Journal, Volume 8, 598 (1995).

[0026] The alkyl and/or alkenyl oligoglycosides may derive from aldosesand/or ketoses having 5 or 6 carbon atoms, preferably from glucose. Thepreferred alkyl and/or alkenyl oligoglycosides are therefore alkyland/or alkenyl oligoglucosides.

[0027] The alkyl radical R⁵ may derive from primary saturated alcohols.Typical examples are 1-butanol, caproyl, enanthyl, caprylyl, pelargonyl,and capryl alcohol, 1-undecanol, lauryl alcohol, 1-tridecanol, myristylalcohol, 1-pentadecanol, cetyl alcohol, palmityl alcohol,1-heptadecanol, stearyl alcohol, isostearyl alcohol, 1-nonadecanol,arachidyl alcohol, 1-heneicosanol, and behenyl alcohol, and also theirtechnical-grade mixtures, as obtained, for example, in the hydrogenationof technical-grade fatty acid methyl esters or in the course of thehydrogenation of aldehydes from the Roelen oxo process.

[0028] The alkenyl radical R⁵ may derive from primary unsaturatedalcohols. Typical examples of unsaturated alcohols are undecen-1-ol,oleyl alcohol, elaidyl alcohol, ricinoleyl alcohol, linoleyl alcohol,linolenyl alcohol, gadoleyl alcohol, arachidonyl alcohol, erucylalcohol, brassidyl alcohol, palmoleyl alcohol, petroselinyl alcohol,arachyl alcohol, and also their technical-grade mixtures, which may beobtained as described above.

[0029] Preference is given to alkyl and/or alkenyl radical R⁵ whichderive from primary alcohols having from 6 to 16 carbon atoms.

[0030] Particularly suitable are alkyl oligoglucosides of chain lengthC₈-C₁₀ which are obtained as an initial fraction in the distillativeseparation of technical-grade C₈-C₁₈ coconut fatty alcohol and may havean impurities fraction of less than 6% by weight of C₁₂ alcohol, andalso alkyl oligoglucosides based on technical-grade C_(9/11) oxoalcohols.

[0031] The alkyl and/or alkenyl radical R⁵ may further derive fromprimary alcohols having from 12 to 14 carbon atoms.

[0032] The index p in the general formula (II) indicates the degree ofoligomerization (DP), i.e., the distribution of monoglycosides andoligoglycosides, and stands for a number between 1 and 10. While p in agiven compound must always be integral and in this case may adopt inparticular the values p=1 to 3, the value p for a particular alkyloligoglycoside is an analytically determined arithmetic variable whichusually represents a fractional number.

[0033] Preference is given to using alkyl and/or alkenyl oligoglycosideshaving an average degree of oligomerization p of from 1.1 to 2.0. From aperformance standpoint, preference is given to those alkyl and/oralkenyl oligoglycosides whose degree of oligomerization is less than 2.0and is in particular between 1.2 and 1.7.

[0034] It is preferred to use alkyl and/or alkenyl oligoglycosides ofthe formula (II) in which p stands for numbers from 1 to 3 and R⁵ standsfor an alkyl radical having from 6 to 16 carbon atoms.

[0035] In one preferred embodiment the detergents and cleaning productsof the invention contain from 0.01 to 25% by weight, preferably from0.025 to 20% by weight, and in particular from 0.1 to 15% by weight ofhydroxy mixed ethers of the formula (I) calculated as active substance,based on the compositions. Active substance is defined as the mass ofsurfactants (calculated as pure material at 100%) which are present inthe detergent and cleaning product.

[0036] In a further embodiment the detergents and cleaning products ofthe invention contain from 0.01 to 30% by weight, preferably from 0.1 to20% by weight, and in particular from 0.2 to 15% by weight of alkyland/or alkenyl oligoglycosides of the formula (II) calculated as activesubstance, based on the compositions.

[0037] Nonionic Surfactants

[0038] The compositions of the invention may comprise further nonionicsurfactants. Typical examples of nonionic surfactants are alkoxylates ofalkanols, endgroup-capped alkoxylates of alkanols without free OHgroups, alkoxylated fatty acid lower alkyl esters, amine oxides,alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acidamide polyglycol ethers, fatty amine polyglycol ethers, alkoxylatedtriglycerides, mixed ethers and mixed formals, fatty acidN-alkylglucamides, protein hydrolysates (particularly plant productsbased on wheat), polyol fatty acid esters, sugar esters, sorbitanesters, and polysorbates. Where the nonionic surfactants containpolyglycol ether chains, these may have a conventional but preferablyhave a narrowed homolog distribution.

[0039] Preferably the further nonionic surfactants are selected from thegroup formed by alkoxylates of alkanols, especially fatty alcoholpolyethylene glycol/polypropylene glycol ethers (FAEO/PO) of the formula(III) and fatty alcohol polypropylene glycol/polyethylene glycol ethers(FAPO/EO) of the formula (IV), endgroup-capped alkoxylates of alkanols,especially endgroup-capped fatty alcohol polyethyleneglycol/polypropylene glycol ethers and endgroup-capped fatty alcoholpolypropylene glycol/polyethylene glycol ethers, and fatty acid loweralkyl esters and amine oxides.

[0040] Fatty Alcohol Polyethylene Glycol/Polypropylene Glycol Ethers

[0041] In one preferred embodiment use is made of fatty alcoholpolyethylene glycol/polypropylene glycol ethers of the formula (III):

R⁶O(CH₂CH₂O)_(n)[CH₂(CH₃)CHO]_(m)R⁷  (III)

[0042] with or without end group capping, in which R⁶ stands for analkyl and/or alkenyl radical having from 8 to 22 carbon atoms, R⁷ for Hor an alkyl radical having from 1 to 8 carbon atoms, n for a number from1 to 40, preferably from 1 to 30, in particular from 1 to 15, and m for0 or a number from 1 to 10.

[0043] Fatty Alcohol Polypropylene Glycol/Polyethylene Glycol Ethers

[0044] Likewise suitable are fatty alcohol polypolypropyleneglycol/polyethylene glycol ethers of the formula (IV):

R⁸O[CH₂(CH₃)CHO]_(q)(CH₂CH₂O)_(r)R⁹  (IV)

[0045] with or without end group capping, in which R⁸ stands for analkyl and/or alkenyl radical having from 8 to 22 carbon atoms, R⁹ for Hor an alkyl radical having from 1 to 8 carbon atoms, q for a number from1 to 5, and r for a number from 0 to 15.

[0046] In accordance with one preferred embodiment, the compositions ofthe invention comprise fatty alcohol polyethylene glycol/polypropyleneglycol ethers of the formula (III) in which R⁶ stands for an aliphatic,saturated, straight-chain or branched alkyl radical having from 8 to 16carbon atoms, n for a number from 1 to 10, and m for 0 and R⁷ forhydrogen. These are adducts of from 1 to 10 mol of ethylene oxide withmonofunctional alcohols. Suitable alcohols are the above-describedalcohols such as fatty alcohols, oxo alcohols and guerbet alcohols. Alsosuitable are, among such alcohol ethoxylates, those which have anarrowed homolog distribution.

[0047] Further suitable representatives of endgroup-uncappedrepresentatives are those of the formula (III) in which R⁶ stands for analiphatic, saturated, straight-chain or branched alkyl radical havingfrom 8 to 16 carbon atoms, n for a number from 2 to 7, m for a numberfrom 3 to 7, and R⁷ for hydrogen. These are adducts of monofunctionalalcohols of the type already described alkoxylated first with from 2 to7 mol of ethylene oxide and then with from 3 to 7 mol of propyleneoxide.

[0048] The endgroup-capped compounds of the formula (III) are cappedwith an alkyl group having from 1 to 8 carbon atoms (R⁷). In many cases,compounds of this kind are referred to in the literature as mixedethers. Suitable representatives are methyl-capped compounds of theformula (III) in which R⁶ stands for an aliphatic, saturated,straight-chain or branched alkyl radical having from 8 to 16 carbonatoms, n for a number from 2 to 7, m for a number from 3 to 7, and R⁷for a methyl group. Compounds of this kind can be prepared easily byreacting the corresponding endgroup-uncapped fatty alcohol polyethyleneglycol/polypropylene glycol ethers with methyl chloride in the presenceof a base.

[0049] Suitable representatives of alkyl-capped compounds are those ofthe formula (III) in which R⁶ stands for an aliphatic, saturated,straight-chain or branched alkyl radical having from 8 to 16 carbonatoms, n for a number from 5 to 15, m for 0, and R⁷ for an alkyl grouphaving from 4 to 8 carbon atoms. Preferably, endgroup capping is carriedout with a straight-chain or branched butyl group by reacting thecorresponding fatty alcohol polyethylene glycol ether with n-butylchloride or with tert-butyl chloride in the presence of bases.

[0050] Instead of the compounds of the formula (III) or in a mixturewith them it is possible if desired for endgroup-capped fatty alcoholpolypropylene glycol/polyethylene glycol ethers of the formula (IV) tobe present. Compounds of this kind are described, for example, in theGerman laid-open specification DE-A1-4323252. Particularly preferredrepresentatives of the compounds of the formula (IV) are those in whichR⁸ stands for an aliphatic, saturated, straight-chain or branched alkylradical having from 8 to 16 carbon atoms, q for a number from 1 to 5, rfor a number from 1 to 6, and R⁹ for hydrogen. They are preferablyadducts of from 1 to 5 mol of propylene oxide and of from 1 to 6 mol ofethylene oxide with monofunctional alcohols, which have already beendescribed as being suitable in connection with the hydroxy mixed ethers.

[0051] Alkoxylated Fatty Acid Lower Alkyl Esters

[0052] Suitable alkoxylated fatty acid lower alkyl esters includesurfactants of the formula (V):

R¹⁰CO—(OCH₂CHR¹¹)_(w)OR¹²  (V)

[0053] in which R¹⁰CO stands for a linear or branched, saturated and/orunsaturated acyl radical having from 6 to 22 carbon atoms, R¹¹ forhydrogen or methyl, R¹² for linear or branched alkyl radicals havingfrom 1 to 4 carbon atoms, and w for numbers from 1 to 20. Typicalexamples are the formal insertion products of on average from 1 to 20and preferably from 5 to 10 mol of ethylene oxide and/or propylene oxideinto the methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl estersof caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid,lauric acid, isotridecanoic acid, myristic acid, palmitic acid,palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid,petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid,arachic acid, gadoleic acid, behenic acid, and erucic acid, and alsotheir technical-grade mixtures. The products are normally prepared byinserting the alkylene oxides into the carbonyl ester linkage in thepresence of specific catalysts, such as calcined hydrotalcite, forexample. Particular preference is given to reaction products of onaverage from 5 to 10 mol of ethylene oxide into the ester linkage oftechnical-grade coconut fatty acid methyl esters.

[0054] Amine Oxides

[0055] As amine oxides it is possible to use compounds of the formula(VI) and/or (VII):

[0056] The preparation of the amine oxides of the formula (VI) involvesstarting from tertiary fatty amines containing at least one long alkylradical and oxidizing them in the presence of hydrogen peroxide. In theamine oxides of the formula (VI) that are contemplated in the context ofthe invention, R¹³ stands for a linear or branched alkyl radical havingfrom 6 to 22, preferably from 12 to 18, carbon atoms, and R¹⁴ and R¹⁵stand independently of one another for R¹³ or an optionallyhydroxy-substituted alkyl radical having from 1 to 4 carbon atoms. It ispreferred to use amine oxides of the formula (VI) in which R¹³ and R¹⁴stand for C_(12/14) and/or C_(12/18) cocoalkyl radicals and R¹⁵ denotesa methyl or a hydroxyethyl radical. Likewise preferred are amine oxidesof the formula (VI) in which R¹³ stands for C_(12/14) and/or C_(12/18)cocoalkyl radicals and R¹⁴ and R¹⁵ have the definition of a methyl orhydroxyethyl radical.

[0057] Further suitable amine oxides are alkylamido-amine oxides of theformula (VII) in which the alkylamido radical R²³CONH comes aboutthrough the reaction of linear or branched carboxylic acids, preferablyhaving from 6 to 22, more preferably having from 12 to 18, carbon atoms,in particular of C_(12/14) and/or C_(12/18) fatty acids with amines. R²⁴represents a linear or branched alkylene group having from 2 to 6,preferably from 2 to 4, carbon atoms and R¹⁴ and R¹⁵ have the definitionindicated in formula (VI).

[0058] The further nonionic surfactants may be present in thecompositions of the invention in amounts of from 0.1 to 15% by weight,preferably from 0.5 to 10% by weight, in particular from 1 to 8% byweight, calculated as active substance, based on the compositions.

[0059] In accordance with the present invention, the detergents andcleaning products may comprise anionic surfactants.

[0060] Anionic Surfactants

[0061] Typical examples of anionic surfactants are soaps,alklylbenzenesulfonates, secondary alkanesulfonates, olefinsulfonates,alkyl ether sulfonates, glycerol ether sulfonates, α-methyl estersulfonates, sulfo fatty acids, alkyl and/or alkenyl sulfates, alkylether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates,monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono-and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates,sulfotriglycerides, amide soaps, ether carboxylic acids and saltsthereof, fatty acid isethionates, fatty acid sarcosinates, fatty acidtaurides, N-acyl amino acids such as, for example, acyl lactylates, acyltartrates, acyl glutamates and acyl aspartates, alkyl oligoglucosidesulfates, protein fatty acid condensates (especially plant productsbased on wheat), and alkyl (ether) phosphates. Where the anionicsurfactants contain polyglycol ether chains, these chains may have aconventional or, preferably, a narrowed homolog distribution.

[0062] Preferred anionic surfactants are selected from the group formedby alkyl and/or alkenyl sulfates, alkyl ether sulfates,alkylbenzenesulfonates, monoglyceride (ether) sulfates andalkanesulfonates, especially fatty alcohol sulfates, fatty alcohol ethersulfates, secondary alkanesulfonates, and linear alkylbenzenesulfonates.

[0063] Alkyl and/or Alkenyl Sulfates

[0064] Alkyl and/or alkenyl sulfates, frequently also referred to asfatty alcohol sulfates, are the sulfation products of primary alcohols,conforming to the formula (VIII):

R¹⁶O—SO₃X  (VIII)

[0065] in which R¹⁶ is a linear or branched, aliphatic alkyl and/oralkenyl radical having from 6 to 22, preferably from 12 to 18, carbonatoms, and X is an alkali metal and/or alkaline earth metal, ammonium,alkylammonium, alkanolammonium or glucammonium.

[0066] Typical examples of alkyl sulfates that may be used in thecontext of the invention are the sulfation products of caproyl alcohol,caprylyl alcohol, capryl alcohol, 2-ethylhexyl alcohol, lauryl alcohol,myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol,isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinylalcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, and erucylalcohol, and also their technical-grade mixtures obtained byhigh-pressure hydrogenation of industrial methyl ester fractions oraldehydes from the Roelen oxo process. The sulfation products may beused preferably in the form of their alkali metal salts and inparticular of their sodium salts. Particular preference is given toalkyl sulfates based on C_(16/18) tallow fatty alcohols or vegetablefatty alcohols of comparable carbon chain distribution in the form oftheir sodium salts.

[0067] Alkyl Ether Sulfates

[0068] Alkyl ether sulfates (“ether sulfates”) constitute known anionicsurfactants which are prepared industrially by SO₃ or chlorosulfonicacid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethersand subsequent neutralization. Ether sulfates suitable in the context ofthe invention are those which conform to the formula (IX):

R¹⁷O—(CH₂CH₂O)_(a)SO₃X  (IX)

[0069] in which R¹⁷ is a linear or branched alkyl and/or alkenyl radicalhaving from 6 to 22 carbon atoms, a stands for numbers from 1 to 10, andX is an alkali metal and/or alkaline earth metal, ammonium,alkylammonium, alkanolammonium or glucammonium. Typical examples are thesulfates of adducts of on average from 1 to 10 and in particular from 2to 5 mol of ethylene oxide with caproyl alcohol, caprylyl alcohol,2-ethylhexyl alcohol, capryl alcohol, lauryl alcohol, isotridecylalcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearylalcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol,petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenylalcohol, erucyl alcohol, and brassidyl alcohol, and also theirtechnical-grade mixtures in the form of their sodium and/or magnesiumsalts. The ether sulfates may have either a conventional or a narrowedhomolog distribution. Particularly preferred is the use of ethersulfates based on adducts of on average from 2 to 3 mol of ethyleneoxide with technical-grade C_(12/14) and/or C_(12/18) coconut fattyalcohol fractions in the form of their sodium and/or magnesium salts.

[0070] Alkylbenzenesulfonates

[0071] Alkylbenzenesulfonates conform preferably to the formula (X):

R¹⁸—Ph—SO₃X  (X)

[0072] in which R¹⁸ is a branched or, preferably, linear alkyl radicalhaving from 10 to 18 carbon atoms, Ph is a phenyl radical, and X is analkali metal and/or alkaline earth metal, ammonium, alkylammonium,alkanolammonium or glucammonium. Preference is given to usingdodecylbenzenesulfonates, tetradecylbenzenesulfonates,hexadecylbenzenesulfonates, and their technical-grade mixtures in theform of the sodium salts.

[0073] Monoglyceride (Ether) Sulfates

[0074] Monoglyceride sulfates and monoglyceride ether sulfatesconstitute known anionic surfactants which may be obtained in accordancewith the relevant methods of preparative organic chemistry. They areusually prepared starting from triglycerides, which as they are orfollowing ethoxylation are transesterified to the monoglycerides andsubsequently sulfated and neutralized. It is likewise possible to reactthe partial glycerides with suitable sulfating agents, preferablygaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP0561999 B1 (Henkel)]. The neutralized substances may, if desired, besubjected to ultrafiltration in order to reduce the electrolyte contentto a desired level [DE 4204700 A1 (Henkel)]. Reviews of the chemistry ofthe monoglyceride sulfates have appeared, for example, from A. K. Biswaset al. in J. Am. Oil. Chem. Soc. 37, 171 (1960) and F. U. Ahmed J. Am.Oil. Chem. Soc. 67, 8 (1990). The monoglyceride (ether) sulfates for usein the context of the invention conform to the formula (XI):

[0075] in which R¹⁹CO is a linear or branched acyl radical having from 6to 22 carbon atoms, c, d and e in total stand for 0 or for numbers from1 to 30, preferably from 2 to 10, and X is an alkali metal or alkalineearth metal. Typical examples of monoglyceride (ether) sulfates suitablein the context of the invention are the reaction products of lauricmonoglyceride, coconut fatty acid monoglyceride, palmitic monoglyceride,stearic monoglyceride, oleic monoglyceride and tallow fatty acidmonoglyceride, and also their ethylene oxide adducts with sulfurtrioxide or chlorosulfonic acid in the form of their sodium salts. It ispreferred to use monoglyceride sulfates of the formula (XI) in whichR¹⁹CO is a linear acyl radical having from 8 to 18 carbon atoms.

[0076] Alkanesulfonates

[0077] By alkanesulfonates are meant compounds of the formula (XII):

[0078] R²⁰ and R²¹ stand for alkyl radicals, and R²⁰ and R²¹ togethershould have not more than 50 carbon atoms.

[0079] Appropriately the detergents and cleaning products may containfrom 0.1 to 20% by weight, preferably from 0.25 to 15% by weight, inparticular from 0.4 to 10% by weight of anionic surfactants, calculatedas active substance, based on the compositions. The remainder to 100% byweight of the detergents and cleaning products may be represented byauxiliaries and also water.

[0080] As auxiliaries, the compositions of the invention may contain forexample solubilizers such as cuminesulfonate, ethanol, isopropylalcohol, ethylene glycol, propylene glycol, butyl glycol, diethyleneglycol, propylene glycol monobutyl ether, polyethylene and/orpolypropylene glycol ethers having molar masses of from 600 to1,500,000, preferably having a molar mass of from 400,000 to 800,000, orin particular butyl diglycol. It is also possible for abrasives, such asquartz flour or wood flour or polyethylene abrasives, to be present.

[0081] In many cases, an additional bactericidal effect is desired, andso the compositions may include cationic surfactants or biocides, anexample being glucoprotamine.

[0082] Suitable builders are zeolites, phyllosilicates, phosphates, andalso ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acidand the salts thereof, and also inorganic phosphonic acids.

[0083] Among the compounds which act as peroxy bleaches, particularimportance is possessed by sodium perborate tetrahydrate and sodiumperborate monohydrate. Examples of further bleaches are peroxycarbonate,citrate perhydrates, and H₂O₂-providing peracidic salts of peracids suchas perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. Theyare usually used in amounts of from 0.1 to 40% by weight. Preference isgiven to the use of sodium perborate monohydrate in amounts of from 10to 20% by weight and in particular from 10 to 15% by weight.

[0084] Suitable enzymes include those from the class of the proteases,lipase, amylases, cellulases, and mixtures thereof. Especially suitableactive enzymatic substances are those obtained from bacterial strains orfungi, such as Bacillus subtilis, Bacillus lichenformis and Strptomycesgriseus. It is preferred to use proteases of the subtilisin type, andespecially proteases obtained from Bacillus lentes. Their fraction mayamount to from about 0.1 to 6%, preferably from 0.2 to 2%, by weight.The enzymes may be adsorbed on carrier substances or embedded in coatingsubstances in order to protect them against premature decomposition.

[0085] In addition to monofunctional and polyfunctional alcohols andphosphonates, the compositions may comprise further enzyme stabilizers.For example, from 0.5 to 1% by weight of sodium formate may be used.Also possible is the use of proteases stabilized with soluble calciumsalts, with a calcium content of preferably about 1.2% by weight, basedon the enzyme. However, it is particularly advantageous to use boroncompounds, examples being boric acid, boron oxide, borax, and otheralkali metal borates such as the salts of orthoboric acid (H₃BO₃), ofmetaboric acid (HBO₂), and of pyroboric acid (tetraboric acid H₂B₄O₇).

[0086] In the context of use in machine laundering processes, it may beof advantage to add customary foam inhibitors to the compositions.Suitable foam inhibitors contain, for example, known organoolysiloxanesand/or paraffins or waxes. Also present, moreover, may be foamregulators, such as soap, fatty acids, especially coconut fatty acid andpalm kernel fatty acid, for example.

[0087] As thickeners it is possible, for example, to use hydrogenatedcastor oil, salts of long-chain fatty acids, which are used preferablyin amounts of from 0 to 5% by weight and in particular amounts of from0.5 to 2% by weight, examples being sodium, potassium, aluminum,magnesium and titanium stearates or the sodium and/or potassium salts ofbehenic acid, and further polymeric compounds. The latter preferablyinclude polyvinylpyrrolidone, urethanes, and the salts of polymericpolycarboxylates, examples being homopolymeric or copolymericpolyacrylates, polymethacrylates and, in particular, copolymers ofacrylic acid with maleic acid, preferably those composed of from 50 to10% by weight of maleic acid. The relative molecular mass of thehomopolymers is generally between 1,000 and 100,000, that of thecopolymers between 2,000 and 200,000, preferably between 50,000 to120,000, based on the free acid. In particular, water-solublepolyacrylates are also suitable which are crosslinked, for example, withabout 1% of a polyallyl ether of sucrose and which possess a relativemolecular mass of more than 1,000,000. Examples of these are polymersobtainable under the name Carbopol® 940 and 941. The crosslinkedpolyacrylates are used preferably in amounts of not more than 1% byweight with particular preference in amounts of from 0.2 to 0.7% byweight.

[0088] In a further embodiment, preference is given to detergents andcleaning products, particularly compositions for automatic dishwashers,which contain from 0.1 to 15%, preferably from 0.5 to 12%, by weight ofsurfactants which contain hydroxy mixed ethers of the formula (I),contain from 5 to 90%, preferably from 10 to 80%, by weight of builders,from 0.1 to 6% by weight of cleaning product enzyme, optionally from 0.1to 40%, preferably from 0.5 to 30%, by weight of bleaches and additionmaterials. Percent by weight is to be understood as being based on thecomposition.

[0089] The present invention further provides for the use of hydroxymixed ethers for washing and cleaning hard surfaces, preferably withinthe home and in the industrial and institutional sector. Particularlyappropriate is their use in ware cleaners, rinse aids, bathroomcleaners, floor cleaners, cleaners in accordance with the clean showerconcept (e.g., bathroom cleaner which is sprayed onto walls and fittingsbefore and after showering so that water and soap residues run off moreeffectively and so subsequent wiping is unnecessary), cockpit cleaners(automobile, aircraft, boat, motorbike), window cleaners and all-purposecleaners. Hard surfaces include ceramic areas, metal areas, paintedareas, plastics surfaces, and surfaces of glass, stone, concrete,porcelain, and wood.

[0090] Particular preference is given to the use of the hydroxy mixedethers of the invention for washing and cleaning hard surfaces,especially in machine dishwashing detergents and/or rinse aids whichthen have a particularly high plastics compatibility and exhibit a verygood runoff behavior.

[0091] Preference is also given to the use of hydroxy mixed ethers incombination with alkyl and/or alkenyl oligoglycosides in the areas ofcleaning listed up to now.

[0092] Very particular preference attaches to the hydroxy mixed ethersof the invention, alone or in combination with the other surfactantsalready described, for the preparation of solid cleaner formulations.

[0093] The present invention will now be illustrated in more detail byreference to the following specific, non-limiting examples.

EXAMPLES

[0094] Screening Method for Evaluating the Wetting Properties ofSurfactant Solutions for Plastics Materials:

[0095] The wetting properties of surfactant solutions for plastics weredetermined in a simplified screening process in accordance with theconditions/test parameters in a commercially customary machinedishwasher, but without using such a machine.

[0096] In order to evaluate the wetting properties, plastic testspecimens measuring 20×5 cm are cleaned first with 1% strength NaOH andthen with isopropanol. The test specimens pretreated in this way arethen immersed in the test solution and removed again directly.Evaluation is carried out visually by compiling an ordered list and inaccordance with a ratings scale from 1-5. 5 here means that the liquidfilm breaks open spontaneously and wetting is completely eliminated.Rating 5 is obtained when using water. Rating 1 denotes complete wettingof the plastics surface with uniform runoff of the liquid film. Rating 1is obtained when using Na-LAS (e.g., Maranil A 55/COGNIS). Testparameters: Water hardness: 2° d [German hardness] Salt load: 700 ppmTemperature: 60° C. Surfactant concentration: 0.1%

[0097] Test Specimens:

[0098] PP (polypropylene); PE (polyethylene); PC (polycarbonate)

[0099] Table 1 shows the test results, with V1 to V5 showing comparativetests and 1 showing the inventive example. TABLE 1 Wetting properties onplastics Composition in % active substance V1 V2 V3 V4 V5 1 Fattyalcohol C₈-C₁₀ + (3 0.1 PO/40 EO) - 2-hydroxy- dodecyl ether(randomized) Fatty alcohol C₈-C₁₀ + — — — — 0.1 60EO - 2-hydroxydodecylether Fatty alcohol C₈-C₁₀ + — — — 0.1 — 10EO - 2-hydroxydodecyl etherPoly Tergent SLF-18B-45* — — 0.1 — — Maranil A 55 (Na-LAS) — 0.1 — — —Water, 2° d/700 ppm NaCl 100 99.9 99.9 99.9 99.9 99.9 Wetting propertieson plastics Temperature: 60° C./plastic 5 1 3 4 3 2 “PP” Temperature:60° C./plastic 5 1 3 4 3 2 “PE” Temperature: 60° C./plastic 5 1 4 3 3 3“PC”

[0100] In the stress crack corrosion test, the plastic rods are brieflyexposed to the test product by immersion or spraying. Adhering productis not removed. After 24 hours, spraying or immersion is repeated. Intotal, the plastics are exposed to the test medium 5 times. Finalassessment takes place visually after 14 days. The codes are as follows:“1” -unchanged “2” -incipient cracking/small crack “3” -continuous crack“4” -fracture

[0101] The inventive examples is placed there in Table 2 under 1, V1 toV4 showing comparative tests. TABLE 2 Stress crack corrosion testComposition in % active substance V1 V2 V3 V4 1 Fatty alcohol C₈-C₁₀ +(3 PO/40 EO) - 5 2-hydroxydodecyl ether (randomized) Fatty alcoholC₈-C₁₀ + 40EO - — — — 5 — 2-hydroxydodecyl ether Fatty alcohol C₈-C₁₀ +10EO - — — 5 — — 2-hydroxydodecyl ether Poly Tergent SLF-18B-45* — 5 — —— Water, fully deionized 100 95 95 95 95 Stress crack corrosion test onplastics Assessment after 14 days Terez 3010 (ABS) 1** 4 4 3 3 Makrolon3103 (PC) 1 3 3 2 2

[0102] TABLE 3 Melting points/ranges ° C. Fatty alcohol C₈-C₁₀ + (3PO/40 EO) - 32-34 2-hydroxydodecyl ether (randomized) Fatty alcoholC₈-C₁₀ + 60EO - 2-hydroxydodecyl 48 ether Fatty alcohol C₈-C₁₀ + 40EO -2-hydroxydodecyl 43 ether Fatty alcohol C₈-C₁₀ + 30EO - 2-hydroxydodecyl38-39 ether Fatty alcohol C₈-C₁₀ + 10EO - 2-hydroxydodecyl At RT, liquidwith ether turbidities Poly Tergent SLF-18B-45* 27-32

[0103] It will be appreciated by those skilled in the art that changescould be made to the embodiments described above without departing fromthe broad inventive concept thereof. It is understood, therefore, thatthis invention is not limited to the particular embodiments disclosed,but it is intended to cover modifications within the spirit and scope ofthe present invention as defined by the appended claims.

What is claimed is:
 1. A reaction product comprising one or more hydroxymixed ethers corresponding to the general formula (I):R¹O[CH₂CHR⁴O]_(x)[CH₂CHR³O]_(y)CH₂CH(OH)R²  (I) wherein R¹ represents analk(en)yl radical having from 4 to 22 carbon atoms; R² represents analk(en)yl radical having from 2 to 22 carbon atoms; R³ represents ahydrogen or a methyl radical; R⁴ represents a hydrogen or a methylradical; x is from 1 to 40; y is from 1 to 40; and x+y>=1; and whereinthe alkylene units —CH₂CHR³O— and —CH₂CHR⁴O— are in randomized form. 2.The reaction product according to claim 1, wherein the one or morehydroxy mixed ethers have a ratio of ethylene oxide groups to propyleneoxide groups of from 40:1 to 40:5.
 3. The reaction product according toclaim 1, wherein R¹ represents an alk(en)yl radical having from 6 to 16carbon atoms.
 4. The reaction product according to claim 1, wherein R²represents an alk(en)yl radical having from 6 to 16 carbon atoms.
 5. Thereaction product according to claim 1, wherein R¹ and R² eachindependently represents an alk(en)yl radical having from 6 to 16 carbonatoms.
 6. The reaction product according to claim 1, wherein R¹ and R²each independently represents an alk(en)yl radical having from 6 to 16carbon atoms.
 7. A reaction product prepared by reacting a 1,2-epoxycompound of the general formula R²CHOCH₂, wherein R² represents analk(en)yl radical having from 2 to 22 carbon atoms, and a randomlyalkoxylated C₄₋₂₂ alcohol having a ratio of ethylene oxide groups topropylene oxide groups of from 40:1 to 40:5.
 8. A cleaning compositioncomprising: (a) one or more hydroxy mixed ethers corresponding to thegeneral formula (I): R¹O[CH₂CHR⁴O]_(x)[CH₂CHR³O]_(y)CH₂CH(OH)R²  (I) wherein R¹ represents an alk(en)yl radical having from 4 to 22 carbonatoms; R² represents an alk(en)yl radical having from 2 to 22 carbonatoms; R³ represents a hydrogen or a methyl radical; R⁴ represents ahydrogen or a methyl radical; x is from 1 to 40; y is from 1 to 40; andx+y>=1; and wherein the alkylene units —CH₂CHR³O— and —CH₂CHR⁴O— are inrandomized form.
 9. The cleaning composition according to claim 8,further comprising an alk(en)yl oligoglycoside corresponding to thegeneral formula (II): R⁵O—[G]_(p)  (II) wherein R⁵ represents analk(en)yl radical having from 4 to 22 carbon atoms, G represents a sugarradical having 5 or 6 carbon atoms, and p represents a number of from 1to
 10. 10. The cleaning composition according to claim 8, wherein theone or more hydroxy mixed ethers have a ratio of ethylene oxide groupsto propylene oxide groups of from 40:1 to 40:5.
 11. The cleaningcomposition according to claim 9, wherein the one or more hydroxy mixedethers have a ratio of ethylene oxide groups to propylene oxide groupsof from 40:1 to 40:5.
 12. The cleaning composition according to claim 8,wherein R¹ represents an alk(en)yl radical having from 6 to 16 carbonatoms.
 13. The cleaning composition according to claim 8, wherein R²represents an alk(en)yl radical having from 6 to 16 carbon atoms. 14.The cleaning composition according to claim 9, wherein R¹ and R² eachindependently represents an alk(en)yl radical having from 6 to 16 carbonatoms.
 15. The cleaning composition according to claim 9, wherein R¹ andR² each independently represents an alk(en)yl radical having from 6 to16 carbon atoms.
 16. The cleaning composition according to claim 10,wherein R¹ and R² each independently represents an alk(en)yl radicalhaving from 6 to 16 carbon atoms.
 17. The cleaning composition accordingto claim 8, wherein the one or more hydroxy mixed ethers are present inan amount of from 0.01 to 25% by weight, based on the composition. 18.The cleaning composition according to claim 9, wherein the one or morehydroxy mixed ethers are present in an amount of from 0.01 to 25% byweight, based on the composition; and wherein the alk(en)yloligoglycoside is present in an amount of from 0.01 to 30% by weight,based on the composition.
 19. The cleaning composition according toclaim 10, wherein the one or more hydroxy mixed ethers are present in anamount of from 0.01 to 25% by weight, based on the composition.
 20. Thecleaning composition according to claim 11, wherein the one or morehydroxy mixed ethers are present in an amount of from 0.01 to 25% byweight, based on the composition; and wherein the alk(en)yloligoglycoside is present in an amount of from 0.01 to 30% by weight,based on the composition.
 21. A method comprising: (a) providing acleaning composition; (b) providing one or more hydroxy mixed etherscorresponding to the general formula (I):R¹O[CH₂CHR⁴O]_(x)[CH₂CHR³O]_(y)CH₂CH(OH)R²  (I)  wherein R¹ representsan alk(en)yl radical having from 4 to 22 carbon atoms; R² represents analk(en)yl radical having from 2 to 22 carbon atoms; R³ represents ahydrogen or a methyl radical; R⁴ represents a hydrogen or a methylradical; x is from 1 to 40; y is from 1 to 40; and x+y>=1; and whereinthe alkylene units —CH₂CHR³O— and —CH₂CHR⁴O— are in randomized form; (c)combining the one or more hydroxy mixed ethers and the cleaningcomposition.